CN1784304A - Method of reducing the color contribution of a coated top layer in a multi-layer material - Google Patents

Method of reducing the color contribution of a coated top layer in a multi-layer material Download PDF

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CN1784304A
CN1784304A CNA2004800121528A CN200480012152A CN1784304A CN 1784304 A CN1784304 A CN 1784304A CN A2004800121528 A CNA2004800121528 A CN A2004800121528A CN 200480012152 A CN200480012152 A CN 200480012152A CN 1784304 A CN1784304 A CN 1784304A
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poly
intermediate layer
skin covering
substrate
layer
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约翰·F·格拉夫
詹姆斯·E·皮克特
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General Electric Co
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General Electric Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

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Abstract

Methods to reduce the inherent color contribution of a top layer in a multi-layer article (10) are disclosed. The articles produced thereby have reduced yellowing and thus lower amounts of color compensating pigments and dyes must be added in order to achieve the desired color of the article. The multi-layer material (10) includes a surface film (12), a substrate (14) and an intermediate layer (13) therebetween.

Description

In multilayer material, reduce the method for the color influence of the top layer that applies
Background technology
Technical field
Therefore the method that the application relates to Weatherable multilayer article and the inherent colour of reduction top layer influences (inherent color contribution) in multi-layer product reduces necessary adding goods with the color compensating pigment of acquisition required color and the amount of dyestuff.Wherein these goods will be white, and the application's method has reduced xanthochromia and can obtain brighter white (lighter white).
The association area explanation
Different polymer products have the long term color problem of unstable.The xanthochromia that this causes polymer has reduced its transparency and attraction.Loss of gloss is that another can be along with the undesirable characteristic of time generation.
The xanthochromia of polymer is caused by action of ultraviolet ray that usually this is usually this xanthochromia to be called " photic xanthochromia ".Used and advised the measure of the photic xanthochromia of a large amount of inhibition.Many all relating to, add ultraviolet absorption compound (UVAs) in these measures in polymer.Usually, UVAs is a low molecular weight compound, and it must use with low relatively amount, and 1 weight % at the most usually is with physical property (for example shock strength) and high-temperature behavior (for example heat distortion temperature) deterioration of avoiding polymer.Yet low-level UVAs may be not enough to provide adequately protect, and the photic xanthochromia of polymer still can take place.
A kind of method that the nurse tree grease article avoids photic xanthochromia and loss of gloss is to use the coating of weather-proof second polymer, and term used herein " weather-proof " expression is to the durability of described phenomenon.The coating of being made by the polyester that contains resorcinol arylide unit generally has good weatherability.The aryl compound part contains the mixture of isophthalic acid ester, terephthalate, particularly isophthalic acid ester and terephthalate units usually.The polyester of the mixture chain unit (chain member) of resorcinol and isophthalic acid ester and terephthalate generally has good weatherability, and can provide the protection to photic xanthochromia after applying on the resin base.
The polyester that contains resorcinol arylate chain members is by as U.S. Patent No. 4,127,560 and Japanese Kokai 1/201,326 disclosed fusion method prepare.This method can provide the polyester that contains isophthalic acid ester and terephthalate chain unit, but does not allow to add the terephthalate greater than 30 moles of %.In addition, the gained polyester has light yellow to amber color, and this color is unacceptable in many cases.
The polyester that contains resorcinol arylate chain members is by the preparation of interface method.This interface method comprise contain water and at least a basically not with the solvent mixture of the miscible organic solvent of water.According to U.S. Patent No. 3,460,961 and Eareckson, Journal of Polymer Science, vol.XL, pp.399-406 (1959), can be by the interface method at Shui Heshui immiscible solvent for example chloroform or carrene, the stoichiometric proportion of using is cresorcin and m-phthaloyl chloride or paraphthaloyl chloride or its mixture=1: 1, in the presence of sodium hydrate aqueous solution, preparation has the resorcinol arylide polyester of isophthalic acid ester and terephthalate chain unit mixture.
Contain resorcinol isophthalic acid ester and the terephthalate polyester chain unit and the copolyester of binary acid or dihydroxylic alcohols alkylidene chain unit (being called " soft segment " chain unit) and be disclosed in U.S. Patent No. 5,916, in 997.These copolymers have excellent weatherability and pliability.The copolyestercarbonates that comprises resorcinol isophthalic acid ester and terephthalate polyester chain unit and chain carbonic ester unit is disclosed in U.S. Patent No. 6,559,270.These copolymers also have excellent weatherability, and compatible with Merlon when blend.
Think that the good weatherability properties major part of the polyester that contains resorcinol arylide unit is to come from shield effectiveness, described polymer can be provided in ultraviolet (UV) light.When being exposed to ultraviolet light, comprise that the polymer of resorcinol arylate chain members can experience photochemistry Fries rearrangement, at least a portion polymer is converted into neighbour-dihydroxy benaophenonel type chain unit from polyester chain unit.Neighbour-dihydroxy benaophenonel type chain unit plays other ultraviolet light of shielding and protects the effect of the ultraviolet sensitivity component in the composition that contains the resorcinol arylide.The good weatherability properties that comprises the polymer of resorcinol arylate chain members is specially adapted in blend and the multi-layer product them, and wherein said polymer can be used as the more protective layer of sensitive substrate component.
People such as Cohen exist, J.Poly.Sci., Part A-1,9, described the multi-layer product that contains the layer of making by the polyester that contains the resorcinol arylide among the 3263-3299 (1971), and some relates to the United States Patent (USP) of MonsantoCompany, comprise United States Patent(USP) Nos. 3,444,129,3,460,961,3,492,261 and 3,503,779.Wherein the method for the weather-proof polymer of application of Pi Luing is to apply by solution, and then evaporating solvent carries out.
Japan Kokai 1/199,841 disclose the goods that comprise basalis and gas curtain coating, this basalis comprises at least 90 moles of % PETGs, this coating is the polyester of resorcinol and M-phthalic acid, and the optional copolyesters unit that has derived from another kind of dicarboxylic acids, this dicarboxylic acids is, for example dicarboxylic acids of terephthalic acid (TPA), naphthalenedicarboxylic acid or various other concrete names.Disclosed goods can prepare by sequence of operations, comprise the coextrusion molding that carries out with melt fully basically, have overcome thus with solution to apply some relevant problem.
Weather-proof polymer is applied to goods and need not to use other method of solvent is known, and comprises U.S. Patent No. 6,572, the 956 disclosed methods of using coating with melt.
In multilayer material, must in one or more layers, add pigment and dyestuff, so that material obtains required color.If one or more layers in these layers is to be made by the material with intrinsic primary colours (for example yellow hue), then must add other colouring agent (being pigment and dyestuff) so that these intrinsic primary colours of compensation.Although using a problem of resorcinol class arylide in multi-layer product is that they can improve the patience of resin base to photic xanthochromia, resorcinol class arylide itself often has the tone of jaundice.
Therefore, be included in the white multi-layer product that its top layer has intrinsic yellow hue material, must add other blueness and red stain, so that obtain achromatic white in order to prepare.Yet, add the overall brightness (over-all lightness) that indigo plant and red colouring agent have also reduced color.
At intrinsic primary colours, in the promptly yellow very strong material, might be able to not obtain the to have enough brightness white goods of (being the appreciable reflectivity of goods).In addition, if top layer has intrinsic yellow primary colours and can not add the compensation colouring agent, the amount that for example can not have a negative impact to gloss to be enough to reduce yellow adds colouring agent, by adding compensatory blueness in lower floor one or more layers and red stain becomes more difficult with the problem that obtains brighter white goods.
Wish to prepare and have the multi-layer product of reduction, reduce the amount of the compensation colouring agent that must add thus and make it possible to make brighter white goods from the influence of the color of top layer.
Summary of the invention
The invention provides the multi-layer product of color characteristics weather-proof and that have enhancing.This multi-layer product has at least three layers: substrate, transparent surface film and the transparent intermediate layer between them, the refractive index in this intermediate layer is lower than the refractive index of skin covering of the surface.
One aspect of the present invention comprises multi-layer product, and these goods comprise: one deck comprises the basalis of first material at least; The intermediate layer; With the skin covering of the surface on it, described skin covering of the surface comprises the thermoplastic polyester that is different from described intermediate layer, and wherein skin covering of the surface and intermediate layer all are transparent, and the refractive index in intermediate layer is lower than the refractive index of skin covering of the surface.
Basalis in the goods of the present invention can be any material that can receive the intermediate layer of adhering to.Suitable material comprises metal, pottery, cellulose products and resin.Spendable resin comprises thermosetting polymer, and thermoplastic polymer particularly is no matter and be addition or condensation prepared.
The intermediate layer is the low transparent polymer material of the refractive index of refractive index ratio skin covering of the surface, and its refractive index preferably is lower than the refractive index of substrate.Term used herein " transparent " and " transparency " are used interchangeably, and refer to can transmitted light wave and unscattered material, so that during by this material observation, the material on this material one side can be clearly in sight.The transparent intention of term comprises all grades " near transparent " and transparent polymer.The amount of the gold-tinted that sends from multi-layer product has been reduced in the intermediate layer, has improved the color characteristics of goods thus.In a preferred embodiment, use polymethyl methacrylate as the intermediate layer.
Skin covering of the surface has improved the weatherability and the solvent resistance of goods, and can be used to change the color and the outward appearance of thermoplastic.Transparent surface film is resorcinol polyaryl thing or resorcinol polyaryl composition copolymer preferably, for example isophthalate/terephthalate/resorcinol (" ITR ") polyaryl thing.
Another aspect of the present invention is the method for preparing multi-layer product, comprises the intermediate layer is administered to substrate and application surface film then.Perhaps, the intermediate layer can be applied to skin covering of the surface, then the two be administered to substrate.Preferably, the intermediate layer is served as and skin covering of the surface can be adhered to the adhesive that substrate forms cohesiveness (cohesive) multi-layer product thus.
Another aspect of the present invention is the multi-layer product by method for preparing.In one embodiment, skin covering of the surface, intermediate layer and substrate form multilayer film, then this multilayer film are applied to second substrate.
Description of drawings
Fig. 1 is the light transmission (light transmission) of goods, and these goods comprise suprabasil skin covering of the surface and do not have the intermediate layer.
Fig. 2 is the light transmission of goods, and these goods comprise that suprabasil skin covering of the surface and refractive index are lower than the intermediate layer of the refractive index of skin covering of the surface.
Preferred implementation
Multi-layer product of the present invention includes but not limited to comprise the multi-layer product of the skin covering of the surface of intermediate layer on basalis, the basalis and top, intermediate layer; Comprise basalis, on each side of described basalis, have the multi-layer product of intermediate layer and skin covering of the surface; And comprising basalis, intermediate layer and at least one laminar surface film, the extra interlayer of one deck is between basalis and the intermediate layer or the multi-layer product between intermediate layer and skin covering of the surface at least.Any interlayer can be transparent and/or can contain additive, for example colouring agent or ornament materials, for example sheet metal.If desired, above skin covering of the surface, cover layer be can comprise, wearability or scratch resistance for example are used to provide.Substrate, intermediate layer, skin covering of the surface and interlayer or cover layer arbitrarily overlapping contact the (contiguous superimposed contact) that preferably be adjacent to each other.In one aspect of the invention, afterwards substrate, intermediate layer and skin covering of the surface are administered to second substrate.
First material that comprises basalis in goods of the present invention can be any material that can receive the intermediate layer of adhering to.Suitable material comprises glass, metal, pottery, cellulose products and resin.Operable resin comprises thermosetting polymer, and thermoplastic polymer particularly is no matter be addition or condensation prepared.
Representational metallic substrates comprises those substrates that contain brass, aluminium, magnesium, chromium, iron, steel, copper and other metal or alloy or contain their goods, and these substrates can require to prevent ultraviolet ray or other climatic phenomenon.
Thermoset polymer substrates can comprise derived from following those: epoxides (epoxies), cyanate, unsaturated polyester (UP), dially phthalate, acrylic acid (ester) class, alkyd resins, fluosite (comprising novolac and bakelite), carbamide, urea formaldehyde resin, BMI, PMR resin, benzocyclobutane, hydroxymethylfurans and isocyanates.The present invention also comprises the multi-layer product of the thermosetting base bottom that contains filling, and for example sheet molding compound (SMC) is listed appropriate filler below.
The cellulosic material that can be used as substrate comprise timber, paper, presspaper, fiberboard, flakeboard (particle board), glued board, art paper (construction paper), brown paper, contain the material of like fibrous element.The present invention also comprise at least a cellulosic material and or at least a thermosetting polymer (being preferably the cohesive thermosetting polymer) or at least a thermoplastic polymer (the preferred thermoplastic polymer that reclaims, for example PET or Merlon) blend, or the mixture of at least a thermosetting polymer and at least a thermoplastic polymer.
Suitable condensation polymer substrates comprises aromatic polycarbonate, polyester, polyphenylene oxide and polyamide.Suitable Merlon comprises homopolymerization and the Copolycarbonate that contains the following formula construction unit:
Wherein, each A 1And A 2Be that monocycle divalent aryl and Y are that one of them or two carbon atoms separate A 1And A 2Bridged group.For example, A 1And A 2The unsubstituted phenylene of ordinary representation or its substitutive derivative.Bridged group Y is alkyl the most normally, particularly saturated group, for example methylene, cyclohexylene or isopropylidene.Most preferred Merlon is a bisphenol-a polycarbonate, wherein A 1And A 2Each is an isopropylidene to phenylene and Y naturally.Preferably, the weight average molecular weight of initial polycarbonate is about 5,000 to about 100,000; More preferably, about 15,000 to about 65,000, and most preferably from about 18,000 to about 35,000.Merlon also can be copolyestercarbonates.Except the carbonate unit of formula I, this polymer chain contains ester units, and this ester units contains the A that is connected to aromatic dicarboxylic acid ester group (as isophthalic acid ester and/or terephthalate) usually 1-y-A 2Part.
Can comprise poly-(alkylene dicarboxylic acids ester) as the suitable polyester of substrate, PETG (hereinafter being called " PET " sometimes) particularly, poly-(1,4-butylidene terephthalate) (hereinafter is called " PBT " sometimes), poly-(trimethylene terephthalate) (hereinafter being called " PTT " sometimes), poly-(naphthalene diacid glycol ester) (hereinafter being called " PEN " sometimes), poly-(naphthalene diacid butanediol ester) (hereinafter being called " PBN " sometimes), poly-(cyclohexanedimethanol terephthalate), poly-(cyclohexanedimethanol-altogether-the ethylidene terephthalate) (hereinafter being called " PETG " sometimes) and poly-(1,4-cyclohexane dimethyl-1,4-cyclohexane cyclohexanedimethanodibasic ester) (hereinafter being called " PCCD " sometimes).
Suitable addition polymer substrate comprises the aliphatic olefin of homopolymerization and copolymerization and functionalized olefin polymer, polyethylene for example, polypropylene, poly-(vinyl chloride), poly-(vinyl chloride-altogether-vinylidene chloride), poly-(PVF), poly-(vinylidene fluoride), poly-(vinylacetate), poly-(vinyl alcohol), poly-(vinyl butyral), poly-(acrylonitrile), acrylic polymer, those of (methyl) acrylamide or (methyl) alkyl acrylate for example, for example, gather (methyl methacrylate) (PMMA), polymer with alkenyl aromatic compound, for example polystyrene comprises syndyotactic polystyrene.For the preferred addition polymer of many application is polystyrene, particularly so-called ABS and ASA copolymer, it contains the styrene-acrylonitrile side chain of thermoplasticity, inelastic body, and this side chain is grafted to respectively on the elastomer raw polymer of butadiene and alkyl acrylate.
Also can use the blend of aforementioned polymer.These blends comprise the blend of thermosetting polymer and thermoplastic polymer (for example, polyphenylene oxide, polyphenylene sulfide, polysulfones, PEI or polyester).Thermoplastic polymer makes up with the thermosetting monomer mixture before curing usually.The blend that also comprises cellulosic material and thermosetting and/or thermoplastic polymer.In blend, general preferred thermoplastic blend.Particularly preferably be polyphenylene oxide and blends of polystyrene; The blend of Merlon and polyester, Acrylonitrile Butadiene and/or ASA copolymer; And the blend of polyphenylene oxide and polyamide, polycarbonate-polyester blends most preferably usually.Blend can comprise normally used additive, for example impact modifier, bulking agent etc.
Usually, the preferred thermoplastic that is used for basalis is blend, Acrylonitrile Butadiene and the ASA copolymer of Merlon, Acrylonitrile Butadiene, ASA copolymer and Merlon and polyester.Wherein also can have other thermoplastic polymer, but above-mentioned polymer or blend most preferably constitute its major part.
Substrate also can add filler, the for example quartz of silicate, zeolite, titanium dioxide, stone flour, glass fibre or glass marble, carbon fiber, carbon black, graphite, calcium carbonate, talcum, mica, lithopone, zinc oxide, zirconium silicate, ferriferous oxide, diatomite, calcium carbonate, magnesia, chromium oxide, zirconia, aluminium oxide, pulverizing, calcined clay, talcum, kaolin, asbestos, cellulose, wood powder, cork, cotton and synthetic textile fibres, particularly reinforcer is as glass fibre and carbon fiber; And colouring agent, for example sheet metal, sheet glass and bead, ceramic particle, other polymer beads can be organic and inorganic or organometallic dyestuff and pigment.
When the required color of multi-layer product was white, suitable colouring agent comprised titanium dioxide, zinc oxide, zinc sulphide, zirconium dioxide, white lead, lead sulfate, lead chloride, lead aluminate, O-phthalic lead plumbate, antimony trioxide, bismuth white, tin oxide, white, its combination of tungsten bletilla of manganese.In addition, can add optical brightener, UV stabilizer and light stabilizer to strengthen the brightness of goods.
Following one deck of multi-layer product of the present invention is the intermediate layer that comprises transparent material, and the refractive index of this material is lower than the refractive index of skin covering of the surface.The suitable intermediate layer that the present invention uses comprises the polymer that is essentially aliphatic series.In this polymer, also allow some aromatic group, as long as refractive index within the acceptable range.Suitable polymers comprises: poly-(PVF) and acrylate copolymer; Poly-(vinylidene fluoride) and acrylate copolymer; Poly-(vinyl chloride) and copolymer; Poly-(vinylidene chloride) and copolymer; Poly-(oxidation methylene); Poly-(ethylene oxide); Poly-(propylene oxide); Poly-(vinyl alkyl ethers); Siloxanes comprises poly-(dimethyl siloxane) and their functional derivative; Poly-(alkyl acrylate); Poly-(alkyl methacrylate); Poly-(N-alkylamide); Poly-(chain acid vinyl ester) for example gathers (vinyl acetate), poly-(vinyl butyrate) etc., and mixed ester; The cellulose chain alkanoic acid ester, for example cellulose acetate, cellulose butyrate, cellulose propionate etc., and mixed ester; The cellulose benzoic ether; Polyethylene (all density); The polyethylene ionomer; Polypropylene (all regularities); Polybutene (all regularities); Poly-(isobutene) (all regularities); Poly-(isoprene); Aliphatic polyester, for example poly-(butanedioic acid glycol ester), poly-(caprolactone), poly-(cyclohexyl Dimethylcyclohexyl dicarboxylic acid esters) and dependency structure; Aliphatic polycarbonate, for example poly-(hexa-methylene carbonic ester); Aliphatic urethane, for example aliphatic vulcabond and the product of aliphatic diamine arbitrarily; Poly-(ethene-altogether-propylene) (EPR rubber); Poly-(ethene-altogether-propylene) ionomer; Poly-(vinyl butyral); Poly-(vinyl alcohol); Poly-(methacrylaldehyde); Natural rubber; Poly-(butadiene) rubber; Melamine resin; Lauxite; With aliphatic epoxy tree.In all cases, the term alkyl of use comprises C1-16 hydrocarbon (straight chain, side chain, ring-type and undersaturated), and can comprise the fluorine or chlorine substituting group.In many cases, can use the copolymer of above-mentioned material, copolymer is compared with homopolymers and will be had superior character in some cases.In addition, can use these polymer blend each other or the blend of these polymer and 1-50% aromatic polymer.
Preferably, poly-(alkyl methacrylate) is as intermediate layer, most preferably polymethyl methacrylate (" PMMA ").
The refractive index in intermediate layer is lower than the refractive index of skin covering of the surface, preferably is lower than the refractive index of substrate.Preferably, the refractive index in intermediate layer is less than about 1.60, more preferably about 1.3 to about 1.55.When PMMA was the intermediate layer, refractive index was about 1.49.
Also exist in the transparent surface film of top, intermediate layer in the multi-layer product of the present invention.Preferably, skin covering of the surface is for having derived from 1 the thermoplastic polyester of the construction unit of 3-dihydroxy benzenes organic dicarboxylic acid ester.Suitable polymers for this purpose, particularly arylate polymer are disclosed in U.S. Patent No. 6,143,839.It is most preferred that glass transition temperature is at least about 80 ℃ and the arylate polymer that do not have a crystal melting temperature (be unbodied those).
Arylate polymer is generally 1, and 3-dihydroxy benzenes isophthalate/terephthalate comprises the construction unit of following formula
Wherein, each R 1Be substituting group, particularly halogen or C1-12 alkyl, and p is 0-3, randomly is combined with the construction unit of following formula
Figure A20048001215200112
R wherein 1With p as defined above, and R 2Be divalence C4-12 aliphatic series, the alicyclic or aliphatic alicyclic group that mixes.
For other acidic group, for example (for example butanedioic acid, adipic acid or cyclohexane-1 derived from aliphatic dicarboxylic acid, the 4-dicarboxylic acids) those, or derived from other aromatic dicarboxylic acid for example 1, those of 8-naphthalene dicarboxylic acids also within the scope of the invention, they are present in the coating, and the preferred amount that exists is greater than about 30 moles of %.Also have other polyester within the scope of the invention, this polyester at least a portion can be miscible with the arylate polymer that exists; They are by PBT, PET, PTT and PCCD representative.Yet more generally, coated polymeric is made up of the unit of formula II, randomly is combined with the unit of formula III.
The unit of formula II preferably contains the resorcinol moiety of resorcinol or replacement, wherein any R 1Group preferably C1-4 alkyl is methyl, ethyl, propyl group or butyl.They are primary alkyl and secondary alkyl, more preferably methyl preferably.Most preferred part is a resorcinol moiety, and wherein p is 0, yet is that 1 part also is excellent for p of the present invention.Described resorcinol moiety is preferably bound to isophthalic acid ester and/or terephthalic acid (TPA) ester moiety.
In the soft block units of optional formula III, the resorcinol moiety of resorcinol or replacement once more with and R 2The form that forms ester exists, wherein R 2Be divalence C4-12 aliphatic series, alicyclic or mixed aliphatic series-alicyclic group.Preferred aliphatic series, particularly C8-12 linear aliphatic group.
The arylate polymer that can be used for goods of the present invention can be by conventional esterification preparation known in the art.For example can or under solid conditions, carry out this reaction with interface mode, solution mode, melt mode.The multi-layer product of interfacial preparation condition and preparation thus is disclosed in United States Patent(USP) Nos. 6,306, in 507,6,265,522,6,291,589,6,294,647 and 5,916,997.
According to the present invention can also as arylate polymer be block copolyestercarbonatecomprise, be disclosed in U.S. Patent No. 6,559, in 270.They comprise the block copolymer that comprises the following formula part,
R wherein 1With p as defined above, each R 4Be divalent organic group independently, m be at least about 10 and n be at least about 4.Soft segment part corresponding to formula III also can exist.Therefore arylate blocks also can contain 1 of not replacement or replacement, 3-dihydroxy benzenes part.Most preferred part or resorcinol moiety, wherein p is 0.
Described 1, the 3-dihydroxy benzenes partly is bonded to the aromatic dicarboxylic acid part, and this aromatic dicarboxylic acid part can be monocycle, for example isophthalic acid ester or terephthalate, or many rings, for example naphthalene two acid esters.Preferably, aromatic dicarboxylic acid partly is isophthalic acid ester and/or terephthalate.Described part one or both of can exist.Usually, the two mol ratio with isophthalic acid ester and terephthalate is about 0.25-4.0: 1, be preferably about 0.4-2.5: and 1, more preferably about 0.67-1.5: 1 and most preferably be about 0.9-1.1: 1 ratio existence.
In one embodiment, arylate polymer prepares by the interface method, and contain formula II unit, preferably be about 0.25-4.0: 1 with the mol ratio, be preferably about 0.4-2.5: 1, more preferably about 0.67-1.5: 1 and most preferably be about 0.9-1.1: 1 ratio is combined with resorcinol isophthalic acid ester and terephthalate units.In this embodiment, need not to exist the soft block units of formula IV.If the ratio of formula III unit outside this scope, particularly when they do not comprise isophthalic acid ester or terephthalate, may preferably exist soft block units to promote interfacial preparation.The particularly preferred arylate polymer that contains soft block units is that 8.5: 1.5 to 9.5: 0.5 resorcinol isophthalic acid ester and resorcinol sebacate unit formed by mol ratio.
Can prepare block copolyestercarbonatecomprise by two-step method, wherein 1,3-dihydroxy benzenes (it can be resorcinol (preferably) or alkyl or halo resorcinol) is the following and at least a aromatic dicarboxylic acid chloride at aqueous alkaline reaction condition (aqueousalkaline reactive conditions) at first, preferably isophthaloyl chloride, terephthalyl chloride or the contact of its mixture.Alkali condition is usually by adding alkali metal hydroxide, is generally NaOH and provides.Generally also have catalyst, the most common is tertiary amine, tetra-allkylammonium, four alkane base Phosphonium or six alkyl guanidine halide, also has organic solvent, normally not miscible with water solvent, the preferably aliphatic compounds of chlorination, for example carrene.Therefore, reaction is carried out in 2 phase systems usually.
For the intermediate polyester of hydroxy-end capped (hydroxyl-terminated) is provided, the mol ratio of resorcinol and acyl chlorides is preferably greater than 1: 1; For example be about 1.01-1.90: 1.Alkali can be about 2-2.5 with the mol ratio with carboxylic acid halides: 1 ratio exists.Usually the amount of using based on the carboxylic acid halides catalyst that makes up is about 0.1-10 mole %.Reaction temperature is generally about 25-50 ℃ most.
After the preparation of finishing intermediate polyester, before being separated, be favourable with the aqueous phase as acidified of two-phase system sometimes with weak acid.The organic facies that contains intermediate polyester carried out for second step then, and this second step is the reaction that forms block copolyestercarbonatecomprise.Yet acidifying or separation are not carried out in expection yet, and carry out described second step, and this normally has feasible and does not lose productive rate or purity.
Might all in organic liquid, prepare intermediate polyester, use the alkali that dissolves in described liquid.The suitable alkali that is used for this purposes comprises tertiary amine, for example triethylamine.
The dihydroxy aromatic compounds that second step used has formula HO--R 4--OH, wherein R 4As defined above.General preferred bisphenol-A.Carbonyl halide is preferably phosgene.Reaction can followingly be carried out: according to the interface process (promptly also in 2 phase systems) of this area approval, use suitable interfacial polymerization catalyst and base reagent (once more preferably NaOH), and optional branching agent for example 1,1,1-three (4-hydroxyphenyl)-ethane and/or stopping of chain agent be phenol or to cumyl phenol for example.In order to suppress the scrambling of block copolymer, with pH remain on low-level relatively on, be generally about 5-9 for the initial part of phosgenation reaction; In the aft section of described reaction, pH can increase to about 10-13.
After finishing above-mentioned two reactions, can separate block copolyestercarbonatecomprise by conventional process.These processes can comprise for example anti-solvent deposition, drying and pass through extruding pelletization.It is also contemplated that by other ester formation method and carry out the first step, representative example is as using aromatic diester and 1, and the 3-dihydroxy benzenes carries out ester exchange in solvent or in melt.
The refractive index of skin covering of the surface can be for about 1.65 to about 1.59, and for most of resorcinol polyaryl thing, refractive index is about 1.625.
In a preferred embodiment, skin covering of the surface is the layer of the substantial transparent of resorcinol polyaryl thing or resorcinol polyaryl composition copolymer, the intermediate layer is poly-(methacrylate Arrcostab), PMMA for example, with basalis be Merlon, for example contain poly-(bisphenol a carbonate) of light scattering pigment.
In the method for the invention, the intermediate layer is applied to substrate, then skin covering of the surface is applied to the intermediate layer.Skin covering of the surface can be identical with substrate, but the intermediate layer is different from substrate and skin covering of the surface.Preferably, select the intermediate layer especially so as substrate to be provided and skin covering of the surface between good cohesive.Colouring agent may reside in substrate, skin covering of the surface or the two, but any colouring agent that is added into skin covering of the surface can not influence the transparency of skin covering of the surface.Can by and substrate, skin covering of the surface or the two identical materials intermediate layer of making can also be included between intermediate layer and the skin covering of the surface, between intermediate layer and the substrate, or exist simultaneously.In some embodiments, colouring agent is added in the interlayer.
The appropriate method of using comprises the preparation substrate, then second material is administered in the substrate to form the intermediate layer, then the 3rd material is applied to the intermediate layer to form skin covering of the surface.Perhaps, can form skin covering of the surface,, then substrate is applied to the intermediate layer to its intermediate layer applied.
Goods of the present invention also can or pass through melt method by the solution coating, for example altogether injection moulding, coextrusion on the surface of substrate, cross molding (overmolding), repeatedly impact (multi-shot) injection moulding, sheet molding and placement (placement) intermediate layer material film and be prepared, then be glued together two-layer, usually bonding in injection-moulding device, then in a similar manner skin covering of the surface is administered to the intermediate layer.In some cases, for example multi-layer co-extruded, can produce these layers simultaneously.
The structure that will comprise skin covering of the surface, intermediate layer and interlayer is applied to substrate also within the scope of the invention with melt.This can be by for example using skin covering of the surface filling injection mould, intermediate layer then, and interlayer then, and inject substrate then and finish.By this method, can carry out in-mold decoration (in-molddecoration) or the like.The both sides of basalis can receive these layers, yet are preferred to apply them to only a side usually.
Goods of the present invention also can or use these layers of adhesive lamination to prepare by heat.As mentioned above, can use aliphatic urethane, siloxanes and acrylic polymer, for example poly-(methyl methacrylate) is as the intermediate layer.Because all these materials all are known adhesives, in these embodiments, the intermediate layer will be served as adhesive and be connected skin covering of the surface and substrate, and form the cohesiveness multi-layer product.
In one embodiment, can extrude substrate, apply to its intermediate layer applied, from solution coatings, superficial film is being pressed onto on it then except that after desolvating by solution.Perhaps, can at first form skin covering of the surface, apply to its intermediate layer applied, from solution coatings, be laminated in the substrate two-layer then except that after desolvating by solution.
Preparation comprises the multi-layer product of substrate, intermediate layer and skin covering of the surface, then this multi-layer product is applied to second substrate and is also contained in the present invention.At this moment, second substrate can be any material of the suitable substrate of above-mentioned conduct.
In resin of the present invention, the thickness of each resin bed is the most common as follows: substrate-at least about 125 μ (micron), be preferably at least about 250 μ, more preferably at least about 400 μ; Intermediate layer-about 1-1000 μ is preferably about 5-500 μ and most preferably is about 10-100 μ; Skin covering of the surface-about 2-2,500 μ are preferably about 10-1000 μ and most preferably are about 10-250 μ; Interlayer if exist, is about 2-2, and 500 μ are preferably about 10-250 μ and most preferably are about 50-175 μ, gross thickness-at least about 125 μ, be preferably at least about 250 μ, more preferably at least about 400 μ.
Goods of the present invention are characterised in that the favourable character of basalis and the weatherability of improvement, and the weatherability of this improvement is confirmed by the ultraviolet light resistant of improvement and the color characteristics of gloss retentivity and improvement.According to the present invention, can reduce the painted dosage of compensation that must add in the multi-layer product with the intrinsic primary colours that overcome material.This comprises by the colouring agent that adds less amount obtain the more ability of high brightness in white.
The advantage that has than the intermediate layer of low-refraction is illustrated in Figures 1 and 2.In two figure, multilayer material 10 comprises the skin covering of the surface 12 with intrinsic yellow hue, but does not contain any compensation colouring agent.Substrate 14 contains pigment and dyestuff, and is opaque.The refractive index of skin covering of the surface 12 and substrate 14 much at one or identical.As shown in Figure 1, when not having the intermediate layer, the light that enters material 10 from the top is by skin covering of the surface 12, and arrives substrate 14, is scattered and absorbs at substrate 14 place's light.Scattered light can leave substrate 14 with high angle, and through yellow surfaces film 12, makes it to have long effective optical path length, and therefore more sodium yellow leaves goods, and making these goods is little yellow, even skin covering of the surface 12 can approach.
As shown in Figure 2, in order to reduce the yellow influence that therefore this long effective optical path length also reduce skin covering of the surface 12, refractive index is clipped between substrate 14 and the skin covering of the surface 12 less than the thin transparent intermediate layer 13 of the refractive index of substrate 14 and skin covering of the surface 12.The light that enters material 10 now from the top is through skin covering of the surface 12 and intermediate layer 13, then by colouring agent scattering and absorption in the substrate 14.Can leave the unique of substrate 14 only because the law of refraction (being Snell ' s law) more concentrates on the light on the direction of upper and lower (up and down).The light that does not leave substrate 14 is more propagated on the direction near the surface normal (normal) of material now, and therefore has short effective optical path length and lower yellow influence.
Goods prepared in accordance with the present invention are suitable for many purposes.As mentioned above, this multi-layer product can comprise second or a plurality of substrate.Can comprise outer body panel (body panels) and the parts that are used for the outdoor vehicles and device by goods prepared in accordance with the present invention, the described outdoor vehicles and device comprise automobile, shielded figure, for example mark; Outdoor packing, for example telecommunications and electric connection box; And Application in Building, for example roof parts, wallboard and windowpane (glazing).The present invention further comprises other manufacturing operation to described goods, such as but not limited to molding, in-mold decoration, in enamelling oven, cure, lamination and/or hot forming.
Multi-layer product of the present invention is particularly including the goods that will be exposed in its length of life in the natural or artificial ultraviolet ray, and most particularly outdoor goods, promptly is used for the goods of outdoor application.Suitable goods are enumerated as automobile, truck, the inner assembly of military vehicle and motorcycle or outer assembly comprise panel, four open plate, coaming plate under the car door (rocker panels), ornament (trim), baffle plate, door, movable roof (decklid), luggage-boot lid, cover, hood, top cover, bumper (bumper), instrument board, fence, the mirror cover, the post frosting, outer cover, the main body side foundry goods, wheelhouse portions, hub cap, catch, spolier (spoiler), window-frame, the headlight seat ring, headlight, taillight, the taillight cover, the taillight seat ring, license plate frame, luggage carrier and foot pedal; The cover, cover, plate and the parts that are used for off-premises station motor-car and device, the cover of electronic installation and telecommunication installation; Outdoor use furniture, aircraft component, ship and offshore set-up (comprising ornament, shell and cover), outboard motor cover, depth gauge cover, small water craft, water ship (jet-skis), pond, hot spring, heat channel, ladder, ladder covering; Building and Application in Building, for example ornament, floor, decorated dormer device or the handled thing of windowpane, roof, work top (countertops), window, window; The cloche that is used for the processing of photograph, picture, pictorial poster or display article; Refractor; The sheath of fluorescent lamp; The sleeve protector; Shingle nail, door and door veneer; The figure that protection is arranged; Outdoor and indoor label; The shell, cover, panel and the parts that are used for ATM (ATM); Be used for lawn and garden with tractor, hay mover and instrument casing, cover, panel and the parts of (comprising lawn and garden apparatus); Window decorations and door decorations; Exercise and toy; The casing of snowmoblie, cover, panel and parts; RV panel and parts; Sports ground equipment; Article by plastics-timber preparation of compositions; The golf course marker; Practical hole lid (utility pit cover), calculating hood; The desktop computer cover; The luggable computer cover; The laptop computer cover; The palmtop computer cover; The monitor cover; Print hood; Keyboard; The fax hood; Duplicate hood; Telephone cover; The mobile phone hood; The transmitting set cover; The radio receiver cover; Light fixture; Lighting apparatus; The Network Interface Unit outer cover; The transformer cover; Air conditioner hood; The outsourcing material of public transportation equipment and seat; Covering of train, subway or bus (cladding) and seat; The measuring device cover; Antenna house; The covering of satellite antenna; Apply the helmet and individual protection equipment; Synthetic or the natural fabric that applies; The film and the replica that apply; The printed matter that applies; The dyeing articles that applies; The fluorescent article that applies; The foamed product that applies; With similar application.
Explain the present invention by following non-limiting examples.
Embodiment
Embodiment 1
Layered product 1-A (contrast) is placed on Lexan 140 grade polycarbonates (available from General Electric Company by 10 mil film with resorcinol polyaryl thing, Niskayuna, New York) on the injection molding plates and the preparation, in molded, contain 5% TiO 2 pigment.This resorcinol polyaryl thing is the block copolymer of resorcinol polyaryl thing and BPA Merlon (ratio is 80: 20), and according to U.S.6,559,270 prepare, and are extruded as the film of 10 mil thick.This molded is covered with polishing plate, be placed in the hydraulic press that is equipped with the pressing plate that is heated to 175 ℃, compacting is 3 minutes under 500psi pressure, and 4,000psi suppressed 1 minute down, and 6,000psi suppressed 1 minute down.After the cooling, with resorcinol polyaryl thing film secure adhesion on white polycarbonate substrate.
Prepare layered product 1-B in an identical manner, difference is 1 mil polymethyl methacrylate film is placed between 10 mil resorcinol polyaryl thing films and the white polycarbonate substrate.By 2041 grades of PMMA of Elvacite are dissolved in the chloroform, preparing 20% solution, and use the scraper curtain coating on glass plate, pulling out (draw) 6 mil wet films, dry this film, and prepare the PMMA film of 1 mil thick.
With layered product 1-A and 1-B under ASTM G26 defined terms, be exposed to the aging meter of Atlas Ci35a xenon arc (Atlas material Testing Technology LLC, Chicago, Illinois) in, difference is to use 0.75W/m 2Irradiation.According to ASTM D 1925, by (GretagMacbeth LLC, New Windsor NY) go up reflection and the color of measurement plate, and note with yellowness index at GretagMacbethColorEye 7000a spectrometer.Colo(u)rimetric shift is presented in the following table 1.The yellowness index that combines the layered product (layered product 1-B) of PMMA interlayer changes all the time less than about 2 units of control sample (layered product 1-A).
Table 1
Expose hour Under 340nm, expose KJ/m2 Δ Y1 (ASTM D1925) layered product 2-A Layered product 2-B
120 586 324 1583 18.2 20.2 16.3 18.4
Embodiment 2
Process according to embodiment 1, difference was before extruded film 3% benzoxazinone UV absorbent (Cyasorb UV 3638 absorbents (Cytec Industries Inc., West Paterson, NJ)) join resorcinol polyaryl thing-bisphenol-a polycarbonate copolymer.As described in embodiment 1, use resorcinol polyaryl composition copolymer film preparation layered product 2-A and use resorcinol polyaryl thing film and PMMA film preparation layered product 2-B.Sample was exposed to visible light 91 hours, as described in embodiment 1, is exposed in the aging meter of xenon arc then.Colo(u)rimetric shift is presented in the following table 2.The yellowness index that combines the layered product of PMMA interlayer changes little about 2 units of product in the same old way of comparison all the time.
Table 2
Expose hour Under 340nm, expose KJ/m2 Δ Y1 (ASTM D1925) layered product 2-A Layered product 2-B
263 764 1400 709 2064 3780 8.2 10.1 12.0 6.5 8.3 10.2
Though described the present invention with exemplary embodiment, the detailed content shown in being not intended to be confined to is because can carry out various improvement and replacement and break away from spirit of the present invention never in any form.Therefore, use routine test, further improvement that this paper is disclosed and equivalent of the present invention are possible for those of ordinary skills, all these improve and equivalent all in claim of the present invention institute restricted portion.

Claims (10)

1. multi-layer product comprises:
At least one deck comprises the substrate of first material;
The intermediate layer; With
The skin covering of the surface that comprises the thermoplastic polyester that is different from described intermediate layer,
Wherein skin covering of the surface and intermediate layer all are transparent, and the refractive index in intermediate layer is lower than the refractive index of skin covering of the surface.
2. the goods of claim 1, the substrate of wherein said one deck at least comprises the addition polymer of at least a Merlon, polyester or alkenyl aromatic compounds.
3. the goods of claim 1, wherein the intermediate layer comprises poly-(PVF) and acrylate copolymer, poly-(vinylidene fluoride) and acrylate copolymer, poly-(vinyl chloride) and copolymer, poly-(vinylidene chloride) and copolymer, poly-(oxidation methylene), poly-(ethylene oxide), poly-(propylene oxide), poly-(vinyl alkyl ethers), siloxanes, poly-(alkyl acrylate), poly-(alkyl methacrylate), poly-(N-alkylamide), poly-(chain acid vinyl ester), cellulose chain alkanoic acid ester, the cellulose benzoic ether, polyethylene, polyethylene ionomer, polypropylene, poly-(butylene), poly-(isobutene), poly-(isoprene), aliphatic polyester, aliphatic polycarbonate, aliphatic urethane, poly-(ethene-altogether-propylene) (EPR rubber), poly-(ethene-altogether-propylene) ionomer, poly-(vinyl butyral), poly-(vinyl alcohol), poly-(methacrylaldehyde), natural rubber, poly-(butadiene) rubber, melamine resin, Lauxite, aliphatic epoxy resin, its copolymer and blend thereof.
4. the goods of claim 1, wherein skin covering of the surface comprises arylate polymer, this arylate polymer contains the resorcinol moiety that is connected to isophthalic acid ester and/or terephthalic acid (TPA) ester moiety.
5. multi-layer product comprises:
At least one deck comprises the substrate of Merlon;
The intermediate layer that comprises poly-(methyl methacrylate); With
The skin covering of the surface that comprises arylate polymer, this arylate polymer comprise the resorcinol moiety that is connected to isophthalic acid ester and/or terephthalic acid (TPA) ester moiety,
Wherein skin covering of the surface and intermediate layer all are transparent, and the refractive index in intermediate layer is lower than the refractive index of skin covering of the surface.
6. claim 1 or 5 goods, wherein skin covering of the surface also comprises at least a colouring agent.
7. claim 1 or 5 goods also comprise the interlayer that is arranged between intermediate layer and the substrate.
8. method for preparing multi-layer product comprises:
Form the substrate of one deck at least of at least a material, this material is selected from glass, metal, pottery, cellulose products and resin;
The intermediate layer is applied in one deck substrate at least; With
Skin covering of the surface is applied to the intermediate layer,
Wherein skin covering of the surface and intermediate layer all are transparent, and the refractive index in intermediate layer is lower than the refractive index of skin covering of the surface.
9. the method for claim 8, the step that wherein prepares multi-layer product is to be undertaken by being selected from following method: solution applies, injection moulding altogether, coextrusion, cross molding, repeatedly impact injection moulding, sheet molding and lamination.
10. the method for claim 8, wherein the step of intermediate layer applied comprises and uses the intermediate layer as adhesive skin covering of the surface to be adhered to the substrate of described one deck at least, forms multi-layer product thus.
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